A valence bond (VB) method is presented and applied to calculate the hidden excited states, 2(1)A(g), and other covalent excited states of polyenes from C4H6 to C28H30. The ground rules needed to understand the results are qualitatively outlined and used to discuss the asymptotic behavior of these molecules as n goes to infinity. The theory enables to understand in a coherent and lucid manner excited state properties, such as the makeup of the various states, their energies and geometries, the puzzling increase of the C=C frequency in the excited state, the opposite bond alternation properties of the ground and excited state, isomerization patterns, soliton characteristics, etc.